Chlorine derivatives of the higher fatty acid alkylolamide acetates



Patented Dec. 16, 1941 CHLORTNE DERIVATIVES OF THE HIGHER FATTY ACID ALKYLOLAMIDE ACETATES Mark Weisberg, Providence, and Louis Corman, Rumford, R. 1., assignors to Alrose Chemical Company, Cranston, it. 1., a corporation of Rhode Island No Drawing.

Application August 6, 1940,

Serial No. 851,842

Claims.

The present invention relates to the production I of new and novel. chlorine derivatives of lower monocarboxylates of the higher fatty acid dialkylolamides, especially stearic diethanol amide acetate. It furthermore relates to the employment of these compounds in the conditioning of textile yarns to render them soft and pliable.

As is well known alkylolamines have been condensed with higher fatty acids in the ratio of 1 moi of the former: 1 mol of the latter, and also 1.5 and more moles of the alkylolamine to 1 mol of the higher fatty acid. Such compounds would not be serviceable as textile softening agents. Kritchevsky who synthesized these condensation products between alkylolamines and higher molecular weight organic acids discovered that one of the chemical properties of the 1:1 types referred to was that they are in general, basic and form salts with any chemicals having acidic groups. as for example, hydrochloric acid, acetic acid and the like (U. S. #2,173,058). Nothing further is stated beyond this categorical remark.

It has been proposed in U. S. Patent No. 2,205,042, to employ the condensation products between alkylolamines and higher fatty acids both before and after treatmentwith acids such as hydrochloric acid and low organic acids as compositions for treating baths to soften textiles. Ranges in reactants is stated to be in the ratio of one moi of the higher fatty acid: -3 moles of the alkylolamine, and %-6 moles of the inorganic or low organic acid.

It is an object of this present invention to produce chlorine containing derivatives of stearic di-,

ethanolamide acetate type compounds by reacting certain types of chlorine-substituted ethane or methane with stearic diethanolamide, said amide being of the type wherein the ratio of the diethanolamine is 1.2 to 2 mols for each mol of the stearic acid; and wherein the quantity of acetic acid added is 2 to 3 times the theoretical necessary for the neutralization of the exces amine of the condensation product. A still further object is to provide conditioning agents which comprise the aforesaid compounds for rendering textile-yarns and fabrics soft and pliable. A still further object is to condition textile yarns and fabrics whereby the yarn is rendered soft and pliable. Another object is to provide a method for the conditioning of textile yarns and fabrics by treating these with a bath containing small amounts ofthese respective softeners.

The following examples illustrate methods of preparing the acetate of stearic diethanolamide and the chlorine-containing derivatives thereof.

EXAMPLE I 284 parts (1 mol) of stearic acid is condensed with 141 parts (1% mol) of diethanolamine for. two to eight hours at l30l80 C. During the reaction approximately 18 parts (1 mol) of water is evolved and 407 parts of a condensation product is formed. This is a relatively soft'yellowish brown wax. This product when dissolved in twice its weight of warm water containing 80 parts of a 56% strength acetic acid yields a material, a

soft cream colored paste, which is valuable as a textile softening agent.

From this example it is seen that an excess of V; moi of the dialkylolamine is used in the reaction with the higher fatty acid. If only sufllcient acetic acid is added that the final product is neutral. slightly wider slightly basic. the product will be actually worthless for use in the textile trade. Thus, ifinstead of employing 80 parts of acid as set forth in the above example, only Y moi of acetic acid 1. e. 35 parts of 56% strength is used to neutralize this condensate, the final product will be practically neutral. But it will have all the detrimental qualities listed in column A of Table I below. On the other hand, if -a minimum of double the theoretical amount of acid required to neutralize the exces amine of the condensate is used in preparing the product, the properties of the same will be far superior to the product made with the theoretical quantity of .acetic acid. Our tests have shownthat a range of acetic acid from two to three times the theoretical amount required to neutralize the excess amine of the condensate is the optimum. In Example I. this would be from 70 to 105 parts of 56% acetic acid.

With reference to Example I it may be desirable to prepare the final softener product in 100% concentration rather than the 31% strength described. In such case glacial acetic acid is used in place of the 56% grade and the water of solution omitted. The glacial acetic acid is added to the molten stearicdiethanolamide base below 100 C., using the same molal proportions of acid and base as described in Example I. The resulting acetate condensate may then be dissolved in approximately twice its weight of warm water to yield a soft cream colored paste.

The table below sets out the effect of concentration of acetic acid in the amide condensation product. The properties of the two respective softeners both made from the initial condensation product of Example I and then standardized to an equal concentration of 31% of condensation product, but one (A) having the theoretical amotmt of acetic acid and the other (13) double the theoretical amount of acetic acid required to neutralize the excess amine therein, are distinctly different, as borne out by the following the soitening hath c y ds. Cl r ty of solutions Turbid. Practically cleari'ar superior in clarity to A.

A and B are equal.

7 Softening powers Whereas these results prove it is important that the concentration of the acetic acid be regulated, it is likewise critical that the ratio of higher fatty acid to the alkylolamine be closely controlled to produce a stable and trade acceptable textile softener. As a result of careful and exhaustive search it has been determined that the condensation products made from a moial ratio of diethanolamine to stearic acid of is the optimum and that ratio is best in the general qualities required of a good textile softener.

Data in Table II below summarizes the results, numerals being selected to designate the rating using 1 as the best The greater numbers indicate proportionately increasing inferiority. It seems advisable to explain that the condensation products were converted into acidified pastes so that the acetic acid in every case bore a constant relation to the total amine content of each condensation product. In this way the pH of the solutions of each respective condensation product was kept reasonably constant.

Team II Efiect of ratio amine to fatty acid in condensate Moi ratio diethanolamino 0.8

stearic acid Softening po 1 Clarity aqueous solutions 3 Stability on boiling aqueous solutions. 4 Rate of solubility in hot water 4 Staining of white goods 3 Completeness of solution in hot water- 3 Eflect on light festness of direct dyed goods The chlorinated derivatives, as indicated supra, of the stearic diethanolamide acetate type com- 180 grams of the stearic diethanolamide condensation product as obtained in Example I by reacting 1 mol of stearic acid with'l fi; moles of diethanolamine is refluxed for four hours at 135 to 140 C. with 36 grams of a polychlor-aliphatic compound such as ethylene dichloride, trichlorethylene, chloroform, carbon tetrachloride, or ethylene chlorhydrin. At the end of this time the oily mixture of amide plus solvent no longer boils vigorously as it did during the early stages 01! the refluxing period. Instead it will be noted that as the reaction between the amide and chlorinated compound nears completion, the oily 5 mixture becomes relatively quiescent, and very little or no appreciable refluxing takes place, in spite of the fact that the temperature of the mixture may be as much as 60 or 70 C. above the boiling point of the chlorinated derivative used.

At the end of the reflux period, the unreacted chlorinated derivative is removed by distilling at a temperature of to C. for not less than one hour by which time the rate of distillation has become negligible or the distillation tube becomes dry. In the case of ethylene chlorhydrin. which has a boiling point (129 C.) which is somewhat higher than the other chlorinated derivatives mentioned, a distilling range of 144 to 158 C. was used for one hour without as much as one drop distilling out of the reaction mass. This indicated that all 01' the ethylene chlorhydrin reacted with the stearic diethanolamide during the reflux procedure.

Table In below summarizes data obtained in experiments run as described in Example II using the various chlorinated compounds mentioned. The amount of stearic diethanolamide condensate used in each run was grams and the amount of chlorinated derivative used in each run was 36 grams.

Team: III

Data on reaction of chlorinated solvents with stearic diethanolamide condensate The aforesaid resulting chlorine containing condensation products are all uniform yellowish brown colored waxes. These are converted into the final softener product in the same general procedure as described in Example I. Thus 400 grams of the condensation product obtained as described in Example II is dissolved in twice its weight of warm water containing 80 grams of 56% strength acetic acid. A soft cream colored paste is obtained. We wish to point out and emphasize moreover that this acetate compoundis superior also to that amide acetate which has not been prepared with these chlorinated ethane or methane derivatives. It excels the textile softening compound obtained by the process described in Example I in the following respects in its technical properties: (1) it possesses better softening powers (2) its rate of solubility in water is much faster (3) it yields clear aqueous havior as the inability to distil off this aliphatic chloride even at temperatures of 50 to 80? 0. above the normal boiling points of these aliphatic chlorine compounds. We do not know much about the nature of the reaction, except that we do know that no chlorine or lwdrogen chloride is liberated. It is perhaps an addition compound of the amide and the ethylene dichloride, ethylene chlorhydrin or like aliphatic chlorinated compounds and may be a quaternary nitrogen compound. But we do not desire to be bound by our beliefs as to the nature of the resulting comp n These aliphatic chlorinated compounds will'react with the stearic diethanol amide type com: pounds derived from the amine and fatty acid in other molal ratios than disclosed in Example II supra. We have made entirely satisfactory reaction products for the subsequent acetic acid treatment wherein the ratio of the amine initially used to fatty acid was prepare a textile softener, but here again our much preferred salt forming acid is acetic. Whereas stearic acid too is the fatty acid we prefer, other higher saturated or unsaturated carboxyiic acids can be used. The concentration of the acetic acid in the final product is a vital factor in these chlorinated derivatives of stearic diethanolamide acetate because a stable and commercially satisfactory textile softening agent is essential.

Without limiting our invention to any particular procedure the following outline will serve to illustrate the application of the softeners herein described to textile fabrics. The general scheme of application can be varied as well as the concentrations of softener in the treating bath. This may depend in part anyway on the structure of the fabric or final hand desired by the finisher of the goods.

A textile fabric is treated at 40 to 80 C. in an aqueous solution containing 0.05% by weight of the softener paste obtaineda's described infExr ample I. The time of immersion of the goods may vary from a few seconds to a few minutes depending on the construction of the fabric, it simply being necessary to evenly wet the fabric through and through. The goods after drying have a marked improvement in appearance, and

' are remarkably smooth and soft to the touch.

By using as a treating bath' for textile fabrics an aqueous solution containing 0.05% by weight of a softener paste prepared (as previously described) from one of the chlorinated wax bases mentioned in Example II, and the aforesaid conditions for processing the goods, 6. very noticeable improvement in softnesasmoothness, and appearance of the treated fabrics, will be obtained. This improvement surpasses that attained when the softener paste secured by the Example I synthesis is employed.

It will be understood that variations maybe made in thesyntheses above set out within the numerical limits set out in the claims; and claims shall be accredited equivalents of reactants of those specifically designated 1. e. other higher saturated or unsaturated acids are the reaction equivalents of stearic acid, and other alkylolamines are reaction equivalents of the specific diethanolamine, and other lower acids are reaction equivalents of acetic acid.

We claim:

1. The process for improving textile yarns and fabrics rendering them soft and smooth which comprises treating them in a bath containing a small amount of a chlorinated derivative of stearic diethanolamide acetate made by reacting a member of the group consisting of ethylene chlorhydrin and polychlor-hydrocarbons of not over two carbon atoms with stearic diethanolamide, said amide being of the kind produced by condensing diethanolamine with stearic acid in the ratio of 1%-2 moles of the amine to 1 mol of the fatty acid, and then admixing this chlorinated amide derivative with acetic acid in an amount which is two to three times the theoretical requirement for neutralizing the excess amine therein.

2. A textile softening agent comprising a chlorinated derivative of stearic diethanolamide acetate made by reacting a member of the group consisting of ethylene chlorhydrin and polychlor-hydrocarbons of not over two carbon atoms with stearic diethanolamide, said amide being of the kind produced by condensing diethanolamine with stearic acid in the ratio of 1%'-2 moles of the amine to 1 mol of.the fatty acid, and then admixing this chlorinated amide derivative with acetic acid in an amount which is two to three times the theoretical requirement for neutralizing the excess amine therein.

3. A textile softening agent comprising a chlorinated derivative of stearic diethanolamide acetate made by reacting a member of the group consisting of ethylene chlorhydrin and polychlorhydrocarbons of not over two carbon atoms with stearic diethanolamide, said amide being of the kind produced by condensing diethanolamine with stearic acid in the ratio of 1 moles of the amine to 1 mole of the fatty acid, and then admixing this chiorinated amide derivative with acetic acid in an amount which is two to three times the theoretical requirement for neutralizing the excess amine therein. a

4. A textile softening agent comprising a chlorinated derivative of stearic diethanolamide acetate made by reacting ethylene chlorhydrin with stearic diethanolamide, said amide being of the kind produced bycondensing diethanolamine with stearic acid in the ratio of 1 -2 moles of the amine to 1 mol of the fatty acid, and then admixing this chlorinated amide derivative with acetic acid in an amount which is two to three times the theoretical requirement for neutralizing the excess amine therein.

5. A textile treating bath comprising an aqueous medium and a small amount of a chlorinated derivative of stearic diethanolamide acetate made by reacting a member of the group consisting of ethylene chiorhydrin and polychlorhydrocarbons of not over two carbon atoms with stearic diethanolamide, said amide being of the kind produced by condensing diethanolamine with stearic acid in the ratio of 156-2 moles of the amine to 1 mol of the fatty acid, and then admixing this chlorinated amide derivative with acetic acid in an amount which is two to three times the theoretical requirement for neutralizing the excess amine therein.

MARK WEISBERG.

LOUIS CORM'AN. 

